Well prepared - good results

APPLICATION NOTE Well prepared - good results No. V-248 Authors Cornelia Küchenmeister-Lehrheuer and Klaus Olddörp Thermo Fisher Scientific, Karlsruhe, Germany Introduction In recent years the demands regarding the reliability of rheological test results have grown significantly, like for most analytical methods. Only if correct test results can be produced and easily be reproduced they can be used for the reliable characterization or comparison of substances. Based on correct test results it is e.g. possible for the QC department to compare different incoming materials or different batches from production no matter whether these results have been produced on different instruments or even on different sites. It is nevertheless essential to use a viscometer or rheometer with a measuring geometry, which gives absolute results, like e.g. coaxial cylinders (CC), parallel plates (PP)- or cone and plate (CP)- geometries. Depending on the sample s nature in can also be necessary to agree upon the test routine and data evaluation method. Every test result contains a certain error, which is the sum of many effects mainly related to the sample, the instrument and the handling. Using the example of PPand CP-geometries, this report will describe the preparation of a rheological test aiming to show the possible errors and how to minimize them. It is assumed that the rheometer has been installed correctly and is properly levelled. Cone or plate? How to choose the right measuring geometry The classical measuring geometries available for Thermo Scientific TM HAAKE TM rheometers have a notched top (Fig. 1). The motor axis contains a pin, which fits into the notch thus allowing the geometry to be mounted only in always the same position relative to the motor s rotor. Fig. 1: Classical measuring geometry with a notched cone (left) and a Connect Assist measuring geometry with a mark on its ceramic shaft for defined mounting (right). The newer Connect Assist measuring geometries have a mark, which can be aligned with a similar mark on the rheometer to achieve the same effect. When a calibration like the MicroStressControl (MSC) [1] is performed to improve the data quality in the low-torque-range (nnm), its results can also be used for later test since the whole setup motor plus measuring geometry is always assembled exactly the same way. Measuring plates, used as the lower part of PP- or CPgeometries are also designed to be mounted only in one position (Fig. 2) [2]. 1

In a CP-geometry, the shear rate is constant over the whole sample, whereas in a PP-geometry the shear rate decreases from its maximum value at the edge to zero at the centre of the geometry. When non-newtonian samples are tested with a PP-geometry, viscosity values always contain an intrinsic error because different parts of the sample are exposed to different shear rates. Therefore if possible, a CP-geometry should be used for viscosity tests. Still, due to the bigger flexibility regarding the measuring gap, PP-geometries are the better and sometimes the only choice for many applications. The diameter of the geometry has to be chosen in relation to the sample s viscosity. For water-like samples it is recommended to use cones or plates with the biggest diameter (60 mm). With increasing viscosity smaller diameters have to be used. For e.g. bitumen or hard rubber an 8 mm plate is often the best choice. recommended to include the auto-matic zero gap determination into the HAAKE RheoWin Job (Fig. 4). This prevents forgetting this important step and leads to a user-independent precisely determined zero gap. For PP- and CP-geometries the correct amount of sample becomes more important for small sample volumes and big edge effects. Therefore to load the correct amount of sample becomes more important for smaller diameters, smaller gaps and higher sample viscosities. Fig. 3: Automatic determination of the zero gap using the monitor mode. Fig. 2: For our PP- and CP-geometries, measuring plates TMP with the corresponding diameters are available. The notch under the mark on the TMP slides over the pin in the temperature control unit for easy and precise positioning. Determination of the zero gap - reference for the measuring gap Whenever a cone, a plate or the lower measuring plate has been mounted, e.g. after it had to be removed from the instrument for cleaning or when a different geometry has been selected, the axial zero point of the geometry has to be determined. In other words, the axial position where the upper part of the measuring geometry touches the lower part is needed as the reference point for the precise setting of the measuring gap. Any error of the zero gap will auto-matically lead to an increased error of the test results due to a wrong gap size during the test. The zero gap can be determined manually using the monitor mode in the Job Manager of the Thermo Scientific TM HAAKE TM RheoWin TM rheometer software (Fig. 3). When using an instrument with an automatic lift (e.g. a Thermo Scientific TM HAAKE TM MARS TM rheometer) it is 1 Fig. 4: Automatic determination of the zero gap using the lift control element during a test run. Here a user-defined message has been activated to ask for the sample to be filled into the geometry. To avoid any error due to thermal expansion or shrinkage of the measuring geometry, the zero gap has to be determined at the temperature, the test is going to be started afterwards. The upper part of the geometry can be put onto the lower measuring plate, which is directly temperature controlled. After the temperature reading remains constant, the upper part of the geometry needs some additional time to adapt to that temperature as well. If

this is done with the upper geometry already mounted, extra care has to be taken that the rheometer s air bearing is not damaged by the expanding geometry for example by setting a small constant normal force. After every part of the measuring geometry has reached the correct temperature, the zero gap can be determined and will be stored as the reference point for the measuring gap. Sample history The pre-treatment or history of the sample can play a crucial role for getting correct and reproducible data. The user has to design the test method keeping in mind that the sample needs to be in thermal and mechanical equilibrium before the rheological test starts i.e. by allowing a sufficiently long waiting time between closing the measuring gap and starting the test. During this time the structure of an e.g. thixotropic sample can recover from the partial destruction during the loading and closing procedure. In some cases it is impossible to reach a stable equilibrium before starting the rheological test. Common examples are samples undergoing a chemical reaction like e.g. glues or coatings. When dealing with such samples, every step of the sample preparation has to be done following always the same sequence and the same timing to start all tests at the same state of the sample in order to get comparable data. In case of samples with a very long structural recovery like for example some thixotropic coatings, a defined pre-shear in the rheometer helps to start the test at least from the same degree of structural damage thus leading to comparable results. Newtonian fluids do not show any of the effects mentioned above. Here the focus only needs to be on correct thermal equilibrium and correct gap filling, which will be looked at in more detail below. Especially when special accessories are used like for example a sample cover with solvent trap to minimize the evaporation of the solvent in the sample or a measuring geometry with a sand-blasted or serrated surface to avoid slipping, the same set up has to be used to yield comparable results. The sample volume needed for the correct filing of a measuring geometry can be found in the HAAKE RheoWin software as part of the geometry s properties (Fig. 5) and in the appendix of the rheometer s manual. Fig. 5: HAAKE RheoWin software displaying the sample volume for correct gap filling. In this example of a cone C35/2 Ti L, all geometry parameters including the gap and the serial number have been read from the geometry after mounting it into the rheometer. Choosing a suitable measuring gap One of the fundamental differences between PP- and CP-geometries is linked to the measuring gap. For every cone only one correct gap exists, equal to truncation of the cone s tip. In case a different gap is needed, a cone with a different cone angle has to be used. For the typical cone angles between 0.5 and 4 the gap is usually in the range between 25 μm and 140 μm. In contrast, the measuring gap of a PP-geometry can be varied within a certain range, so the measuring conditions can be adapted to the sample s properties. The correct measuring gap for any CP- or cylindrical geometry is part of its set of individual parameters, measured and calculated based on its dimensions. After production every part is measured precisely and its diameter, cone angle and truncation are printed into an individual certificate included in the geometry s box. For the classical measuring geometries, these parameters have to be entered manually into HAAKE RheoWin once and from then on are auto-matically available whenever the geometry is used for a test. With the Connect Assist geometries, all relevant parameters will automatically be transmitted to HAAKE RheoWin when the geometry is mounted into the rheometer. For both PP- and CP-geometries the rule applies that the measuring gap has to be at least 5 times the diameter of the biggest particle in the sample to be able to measure the sample as whole. In the worst case some bigger particles could pile up under shear and block the gap leading to very noisy data or even damage the surface of the measuring geometry. For example, a suspension with particles up to 100 μm in diameter needs a gap of at least 500 mm. In this case only a PP-geometry can be used because CP-geometries with an angle bigger than 4 would not comply with the current standards and do therefore not exist. The factor 5 is just a rule of thumb. Depending on the particle s characteristics, it might become necessary to select an even bigger gap. When doing tests on foams or emulsions the measuring gap has to be chosen based on the diameter of the biggest bubbles or droplets. Otherwise the sample s properties could already be changed simply because it is squeezed into the measuring gap. When a sufficiently large measuring gap is used, like e.g. 1 mm with a PP-geometry, any kind of error in parallelism can be neglected due to the tolerance of manufacturing. For very small gaps these small imperfections can lead to an error of the zero gap determination and therefore the measuring gap itself. Either a bigger uncertainty has to be taken into account for test results collected with very small gaps or even greater care has to be invested when producing and adjusting the components for such a test. 2

Sample loading, sample trimming, closing the gap- the optimum gap filling Under ideal conditions, the sample fills the measuring gap completely and without any air bubbles. Around the edge of a PP- or CP-geometry the open sample surface should slightly bulge outwards. Depending on the sample s consistency a suitable tool should be used to fill the sample into the measuring geometry. For low viscous samples a pipette can be used. For samples with a higher viscosity or stronger texture a spatula or spoon is the right tool. Samples with a delicate structure should be sheared as little as possible during the loading procedure to keep damages to the structure as small as possible. In general, the sample should be placed in the centre of the geometry. The optimum amount of sample can be found amongst the parameters for each measuring geometry listed in HAAKE RheoWin (Fig. 5). It is recommended to slightly overfill the geometry first in order to avoid air remaining in the measuring gap after closing it. Underfilling of the measuring gap has to be avoided under all circumstances! After closing the measuring geometry the sample has to be trimmed i.e. the excess of sample that was squeezed out of the gap has to be removed with a suitable tool. Since this procedure leads to a straight sample rim, it is recommended first to go to the trimming position above the measuring gap, trim the sample and then close the geometry thus forming a slightly bulged sample rim. As rule of thumb, a gap 1 5% wider than the measuring position is used as trimming position. After loading the sample this position is set either manually or automatically during a running test method in the HAAKE RheoWin software. For sensitive samples the lift speed should be reduced to minimize the damage to the sample s structure during closing the gap. The tools selected for trimming should be made of a nonabsorptive material to avoid any solvent being sucked out of the sample. Any kind of simple paper or wooden tool is therefore excluded. The tool should have a straight edge to form a clean straight sample surface. Fig. 7: Lower measuring plate TMP with a diameter chosen to match the upper geometry. For a properly trimmed sample the spatula is moved around the whole sample using the side of the lower plate as a guide (Fig. 8a). Afterwards, the rim is checked visually whether all excess has been removed. If necessary, this step has to be repeated. Especially when trimming highly viscous samples, it is possible that a bit of the excess sample gets pushed onto the edge of the upper geometry. During the test procedure this material could flow down again, leading to disturbing edge effects thus having a bad influence on the data quality. Therefore is it recommended, especially for highly viscous samples and geometries with small diameters, to strip the edge of the upper geometry from any remaining material (Fig. 8b). Finally the geometry will move to the measuring position and the sample will get a slightly bulged rim as indicated in Fig. 9. a b Fig. 8: Removing excess sample with a spatula in trimming position; 8b: Removing excess sample from the edge of the upper geometry. Fig. 6: Parallel plate geometry in measurement position without and with sample cover.the trimming position can be set in HAAKE RheoWin. Recommended are 1-5% above the measuring gap chosen for the test (in the example above 100 μm). When the upper geometry approaches the trimming position using HAAKE RheoWin s lift function, the axis of the rheometer is locked to avoid any damage to the sample s structure by an accidental turning of the measuring geometry. The excess sample can be removed with a lab spatula or a special trimming tool [3]. The lower plate shown in Fig. 7 has been chosen to match the upper geometry s diameter, which makes the necessary trimming procedure much easier. Fig. 9: Correct gap filling after closing the measuring geometry. A perfect filling is the ideal basis for generating good data with a rheological test. Examples for such a test have been described in detail in [4] and [5] using the examples of testing a calibration oil and a viscoelastic PDMS standard respectively. 3

Summary For the determination of reliable rheological data the sample and the rheometer have to be prepared and handled care-fully. Apart from selecting the right measuring geometry and determining the correct zero point, there are some steps not directly linked to the rheometer itself, which are crucial for the data quality. The procedure how to prepare the sample into the rheometer and how carefully the sample is trimmed afterwards are at least equally important. Special care is needed when using small measuring geo-metries, small measuring gaps and high viscosities, since in these cases edge effects have a bigger influence on the data quality. In case of small measuring gaps an individual adjustment of all components involved can improve the data quality. Following the recommendations listed in this report, the accuracy and reproducibility of rheological results can be improved significantly. Especially when rheological results have to be compared with results from other departments or other companies, accurate results are an absolute must. References [1] Thermo Fisher Scientific Application note V285 Preparing the Rheometer for Highest Sensivity Tests, Klaus Oldörp (in preparation) [2] Thermo Fisher Scientific Product information P029 Overview parallel plates and cone & plate geometries, Cornelia Küchenmeister-Lehrheuer, Jint Nijman and Fabian Meyer [3] Thermo Fisher Scientific Product information P003 Trimming tool to remove overfilling in a plate/plateand cone/plate-measuring geometry, Küchenmeister-Lehrheuer and Klaus Oldörp [4] Thermo Fisher Scientific Application note V218 Test liquids, Klaus Oldörp [5] Thermo Fisher Scientific Application note V264 Testing a Viscoelastic PDMS Standard in Oscillation, Klaus Oldörp Find out more at thermofisher.com/rheometers For Research ch Use Only.. Not for use in diagnostic procedur ocedures. es. 2017 Thermo Fisher Scientific Inc. All rights reserved. All trademarks are the property of Thermo Fisher Scientific and its subsidiaries unless otherwise specified. V248 0117 2